HETEROCYCLES
An International Journal for Reviews and Communications in Heterocyclic ChemistryWeb Edition ISSN: 1881-0942
Published online by The Japan Institute of Heterocyclic Chemistry
Regular Issue
Vol. 16, No. 11, 1981
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■ First Examples of Isoxazolidin-4-ones
Anup Bhattacharjya*
*Department of Chemistry, Washington University, St. Louis, Missouri 63130, U.S.A.
Abstract
First examples of isoxazoldin-4-ones were prepared from 2,4-dibromo-2,4-dimethylpentan-3-one and hydroxylamine and N-acylhydroxylamines.
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■ Structure-activity Relationships of Oxygenated Morphinas. II. Synthesis and Biological Properties of 4-Methoxymorphinan-6-ones with Narcotic Antagonist Side-chains on Nitrogen
Helmut Schmidhammer, Arthur E. Jacobson, Louise Atwell, and Arnold Brossi*
*Laboratoryof Chemistry, Medical Chemistry Section, National Arthritis Institute, National Institute of Health, Behesda, Maryland 20892, U.S.A.
Abstract
The synthesis of narcotic antagonists from the 4-methoxymorphinan-6-one series is described. The synthesis started from optically active 4-hydroxy-6-keto-N-formylmorphinan prepared from morphine, by employing conventional procedures. The compounds have pentazocine-like agonist activity and N-cyclopropylmethyl-4-methoxymorphinan-6-one is somewhat more potent than nalorphine as a narcotic antagonist.
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■ Isomerization and Hydrogenation of Nitrogen-containing Organic Compounds Catalyzed by Heterogeneous Catalysts
Hideshi Hattori and Kozo Tanabe*
*Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan
Abstract
The double-bond isomerization of 1-N-pyrrolidino-2-propene and N,N-dimethyl-2-propenylamine were studied at 40°C over MgO, CaO, SrO, BaO, La2O3, ThO2, ZrO2, ZnO etc. It was found that MgO and CaO which have strong basic sites on the surfaces exhibited a high catalytic activity, the selectivity for the formation of 1-N-pyrrolidino-1-propene being more than 80 %. The double-bond migration of the allylamines is suggested to proceed via anionic intermediates in which the cis form is much more stable than the trans form. For the hydrogenation of N,N-dimethyl-2-propenylamine, the activity as well as the selectivity of nickel catalysts supported on MgO, CaO, La2O3, ThO2, TiO2, ZrO2 etc. was examined at 0°C. Nickel on MgO was found to give 100 % conversion and almost 100 % selectivity for the formation of N,N-dimethylpropenylamine. It is suggested that nickel catalyst becomes active when supported on basic oxides. The reaction path is discussed on the basis of experiments using deuterium as a tracer.
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■ Synthesis of Quinoline Alkaloids and Related Compounds. Synthesis of Zanthophylline and a New Synthesis of 3,3-Bis(γ,γ-Dimethylallyl)-N-methyl-2,4-dioxo-1,2,3,4-tetrahydroquinoline
Pietro Venturella,* Aurora Bellino, and Maria Luisa Marino
*Instituto de Chimica Organica , Facolta de Scienze, Università digli Studi di Palermo, 20 via Archirafi, 90123 Palermo, Italy
Abstract
The alkaloid zanthophylline (I) was synthesized from the 8-methoxyflindersine (III) by N-alkylation with chloromethylacetate. The 3,3-bis(γ,γ-dimethylallyl)-N-methyl-2,4-dioxo-1,2,3,4-tetrahydroquinoline (II) was also synthesized by direct methylation of (V).
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■ On Cardioactive Steroids V. Synthesis of the Pyridone Analogue of Bufalin
Min-Jen Shiao, Thomas Y. R. Tsai, and Karel Wiesner*
*Natural Products Research Center, Department of Chemistry, University of New Brunswick, Bag Service #45222, Fredericton, New Brunswick, E3b 5A3, Canada
Abstract
An efficient and simple synthesis of azabufalin (2) from compound (4) derived from testosterone is reported.
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■ Reduction of 1-Substituted 3-Oxidopyridiniums
William R. Ashcroft and John A. Joule*
*Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, U.K.
Abstract
1-Substituted 3-oxidopyridiniums are smoothly reduced by sodium borohydride in ethanol to give 1-substituted 3-hydroxypiperidines but much less efficiently by lithium aluminium hydride in hot tetrahydrofuran to give mainly, 1-substituted 5-hydroxypiperid-3-eines.
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■ Novel Syntheses of Dihydrooxazines, Tetrahydropyrimidines and Tetrahydropyridines from Allenyl Nitriles
Stephen R. Landor,* Phyllis D. Landor, Z. Tanee Fomum, and J. Tanyi Mbafor
*Department of Chemistry, Mona Campus, , University of the West Indies, Mona, Kingston 7, Jamaica
Abstract
α-Allenylnitriles give dihydrooxazines and tetrahydropyridines with 3-hydroxypropylamine whereas with 1,3-diaminopropane they afforded tetrahydropyrimidines.
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■ 13C-NMR Shift Increments for 3-Substituted Pyridines
Roger Dommisse, Eddy Freyne, Eddy Esmans, Josef Lepoivre, and Frank Alderweireldt*
*Labratory of Organic Chemistry, University of Antwerp (RUCA), Groenenborgerlaan 171, B-2020 Antwerp, Belgium
Abstract
The 13C-NMR spectra of some 3-substituted and 3,5-disubstituted pyridines are examined. It appears that the shift increments for the 3-acetyl group previously published in the literature were based on a wrong assignment of the spectra. A new set of shift increments for 3- or 5-substituents are derived from the spectra of such compounds, most of which were not described before.
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■ Synthesis of Cannabichromanone
Laura Chiodini, Mauro Di Ciommo, and Lucio Merlini*
*Istituo di Biochimica Generale, Università digli Studi di Milano, Via Venezian 21, 20133 Milano, Italy
Abstract
The synthesis of the cannabis constituent cannabichromanone is reported.
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■ Asymmetric Transformation of 2-Chloroalkanoic Acids via Oxazoline Derivatives
Saizo Shibata,* Hajime Matsushita, Hajime Kaneko, Masao Noguchi, Masahiko Saburi, and Sadao Yoshikawa
*Central Reseasrch Institute, Japan Tobacco Inc., 6-2, Umegaoka, Midori-ku, Yokohama, Kanagawa 227-8512, Japan
Abstract
Asymmetric transformation of 2-chloroalkanoic acids via oxazoline derivatives were examined using (S)-phenylalaninol as a chiral auxiliary. After the transformation optical purities of the acids were appreciably improved compared with those of the acids obtained before the transformation.
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■ How Regioselective Are 1,3-Dipolar Cycloadditions with Carbonyl Ylides?
Jürgen Brokatzky-Geiger and Wolfgang Eberbach*
*Chemusches Laboratorium, Universität Freiburg, Albertstr. 21, D-7800 Freiburg, Germany
Abstract
Several cycloaddition reactions of asymmetrically substituted carbonyl ylides are described.
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■ Tetrahydropyridines in the Prins Reaction: A Novel 3-Oxa-7-azabicyclo[3.3.1]nonane Derivative
Alan Casy* and Francis Ogungbamila
*School of Pharmacy and Pharmacology, University of Bath, Bath, BA2 7AY, U.K.
Abstract
Reaction of tetrahydropyridines obtained by the dehydration of a diastereoisomeric mixture of 1-benzyl-3,4-dimethyl-4-piperidinols with excess of aqueous formaldehyde and sulphuric acid (Prins reaction) gave 7-benzyl-1,9-dimethyl-9-hydroxy-3-oxa-7-azabicyclo[3.3.1]nonane. The stereochemistry of the bicyclic product (cis N/9-OH, piperidine boat-chair) and of the precursor 4-piperidinols is established from nmr (13C and 1H) and ir spectroscopic evidence.
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■ Synthesis of Optically Active 6α-Methoxy Penem
Maurizio Foglio, Giovanni Franceschi,* Cosimo Scarafile, and Pierangelo Zini
*Ricerca&Sviluppo Chimico, Farmitalia Carlo Erba SpA, Via dei Gracchi 35, 20146 Milano, Italy
Abstract
Synthesis of 6α-methoxy-2-acetoxymethyl-2-penem-3-carboxylic acid starting from penicillin V is described.
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■ An New Photochemical Synthetic Route to 2,3-Benzodiazepines from Isoquinoline N-Imides
Michiko Enkaku, Jyoji Kurita, and Takashi Tsuchiya*
*School of Pharmacy, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan
Abstract
Photolysis of the isoquinoline N-imides (6) under a basic condition gave the corresponding 5H-2,3-benzodiazepines (7), which were converted to the 3-acetyl-3H-2,3-benzodiazepines (11) by treatment with acetic anhydride.
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■ Utilization of Sulfoxides Containing Pyridine Nuclei as Phase Transfer Catalysis: III
Naomichi Furukawa, Satoshi Ogawa, Tsutomu Kawai, Keiko Kishimoto, Hisashi Fujihara, and Shigeru Oae*
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
Several sulfoxides bound to pyridine were prepared. These sulfoxides were found to promote nucleophilic substitution reactions of alkyl halides markedly in solid-liquid biphase system.
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■ Novel Rearrangement of 8H-Isoquino[2,1-b][2]benzazocines to 3-Phenylpyrrolo[2,1-a]isoquinolines and Related Compounds
Miyoji Hanaoka,* Akimori Wada, Yasuhiko Sakamoto, Michie Ichihara, Shingo Yasuda, and Takeshi Imanishi
*Faculty of Pharmaceutical Scicences, Kanazawa University, 13-1 Takara-machi, Kanazawa 920-0934, Japan
Abstract
The 8H-isoquino[2,1-b][2]benzazocines (1) were efficiently transformed to the 3-phenylpyrrolo[2,1-a]isoquinolines (3) and related compounds by transannular reactions.
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■ Studies on the Syntheses of Heterocyclic and Natural Compounds. Part 949. A Total Synthesis of (±)-Corynantheidol
Tetsuji Kametani,* Naoaki Kanaya, Toshio Honda, and Masataka Ihara
*Hoshi University, 2-4-41 Ebara, Shinagawa-ku, Tokyo 142-8501, Japan
Abstract
A facile synthesis of (±)-corynantheidol (17) has been achieved by the application of enamine annelation using 3,4-dihydro-1-methyl-β-carboline (5) and dimethyl 3-methoxyallylidenemalonate (6). Stereochemical assignment for catalytic hydrogenation products of the corresponding enamides has also been investigated.
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■ Alternative Syntheses of (±)-Epi- and (±)-Desethyl-ibogamine Using a Diels-Alder Reaction of 1-Benzyl-2(1H)-pyridone
Hiroshi Tomisawa,* Hiroshi Hongo, Hideki Kato, Kumi Sato, and Reiko Fujita
*Tohoku Pharmaceutical University, 4-4-1 Komatsushima, Aoba-ku, Sendai 981-8558, Japan
Abstract
The Diels-Alder reaction of 1-benzyl-2(1H)-pyridone (1) with methyl acrylate (2) gave methyl 2-benzyl-3-oxo-2-azabicyclo[2.2.2]oct-7-ene-6-endo-carboxylate (3) as a main product. Using this compound a short total synthesis of (±)-epi-ibogamine was achieved. (±)-Desethylibogamine was also synthesized formally from the Diels-Alder adduct (11) of 1 with maleic anhydride.
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■ On the Reaction of Ethylene Oxide with cAMP
József Béres,* Ernö Moravcsik, and Lajos Radics
*NMR Laboratory, Central Research Institute of Chemistry, H-1525, Budapest, Hungary
Abstract
Contrary to recent suggestions, proton coupled carbon-13 spectra show that the title reaction occurs on N1 of the base rather than on the phosphate diester group.
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■ Studies of Potential Heterocyclic Sulfones as Antimicrobial Agents. Synthesis and Antimicrobial Activity of Some Novel Substituted Arylsulfonylbenzo[h]quinoline Derivatives
Rajendra Prasad Bahuguna, Yogesh Chandra Joshi, Mahaveer Prasad Dobhal, Bhuwan Chandra Joshi,* and Hari Narain Mangal
*Department of Chemistry, University of Rajasthan, Jaipur 302 004, India
Abstract
A series of substituted arylthiobenzo[h]quinoline (sulfides, Ia~If and IIa~IIc) synthesised earlier were oxidised (with 1% KMnO4) to get their corresponding sulfones (IA~IF and IIA~IIC). All these compounds have been characterised by their elemental analysis, molecular weight determination (Rast Method) and spectral studies (IR and 1H NMR). These compounds have been screened for antimicrobial activity against Gram positive Cocci and Gram negative Bacilli.
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■ Photochemical Reaction of 2-Bromo-3-methoxy-1,4-naphthoquinone with Sily Enol Ether — One-pot Synthesis of Polycyclic Aromatic Compounds
Kazuhiro Maruyama,* Seiji Tai, Masahiro Tojo, and Tetsuo Otsuki
*Department of Chemistry, Faculty of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Abstract
5-Hydroxybenz[a]anthracene, 2-aryl-2,6-dihydroxy-5-fomyl-2,3-dihydronaphtho[1,2-b][1,4]dioxin, and 4-arylnaphtho[2,3-d][1,3]dioxepin derivatives were synthesized by one-pot photochemical reaction of 2-bromo-3-methoxy-1,4-naphthoquinone with trialkylsilylenolether.
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■ Furanomycin Analogs: Optically Active Norfuranomycins
Hosein R. Divanfard, Zenon Lysenko, J. Edward Semple, Pen-Chung Wang, Madeleine M. Joullié,* and John F. Blount
*Department of Chemistry, University of Pennsylvania, 231 South 34th Street Philadelphia, PA 19104-6323, U.S.A.
Abstract
The total synthesis of the four stereoisomeric forms of norfurnanomycin is described. The absolute stereochemistry of these novel amino acids was established by X-ray crystallography.
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■ Synthesis of 5-Hydroxy-3-methyl-3-pyrrolin-2-one [(±)-Jatropham, an Antitumor Alkaloid] and Its 4-Methyl Isomer
Tatsuo Nagasaka,* Sayuri Esumi, Naganori Ozawa, Yoshiyuki Kosugi, and Fumiko Hamaguchi
*School of Pharmacy, Tokyo University of Pharmacy and Life Science, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan
Abstract
5-Hydroxy-3-methyl-3-pyrrolin-2-one (1), which is known as jatropham; an antitumor alkaloid, is conveniently synthesized from succinimide. One step synthesis of 5-hydroxy-4-methyl-3-pyrrolin-2-one (2) by the regioselective reduction of methylmaleimide with NaBH4/H+ is also described.
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■ Preparation and Decomposition of 1,4,6-Trisubstituted 3-Nitroso-tetrahydro-2(1H)-pyrimidinones
Choji Kashima,* Akira Katoh, and Yoshimori Omote
*Department of Chemistry, University of Tsukuba, 1-1-1 Ten-nodai, Tsukuba-shi, Ibaraki, 305-8571, Japan
Abstract
1,4,6-Trisubstituted tetrahydro-2(1H)-pyrimidinones (1) were treated with sodium nitrite in acidic conditions to afford the corresponding 3-nitroso-2(1H)-pyrimidinones (2) in high yields. The decomposition of 2a with potassium hydroxide was also discussed.
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■ The Chemistry of 4,5-Dihydro-5-oxo-1,3-oxazoles
Arya K. Mukerjee* and Pradeep Kumar
*Chemistry Department, Faculty of Science, Banaras Hindu University, Varanasi-221 005, India
Abstract
4,5-Dihydro-5-oxo-1,3-oxazoles are important class of heterocycles and interest in their chemistry continues unabated because of their usefulness as synthons. In this review an attempt has been made to present the chemistry of this class in an integrated form and in proper perspective under the following headings: